A directing group switch in copper-catalyzed electrophilic C-H amination/migratory annulation cascade: divergent access to benzimidazolone/benzimidazole.

We present here a copper-catalyzed electrophilic ortho C-H amination of protected naphthylamines with N -(benzoyloxy)amines, cyclization with the pendant amide, and carbon to nitrogen 1,2-directing group migration cascade to access N , N -disubstituted 2-benzimidazolinones. Remarkably, this highly atom-economic tandem reaction proceeds through a C-H and C-C bond cleavage and three new C-N bond formations in a single operation. Intriguingly, the reaction cascade was altered by the subtle tuning of the directing group from picolinamide to thiopicolinamide furnishing 2-heteroaryl-imidazoles via the extrusion of hydrogen sulfide. This strategy provided a series of benzimidazolones and benzimidazoles in moderate to high yields with low catalyst loading (66 substrates with yields up to 99%). From the control experiments, it was observed that after the C-H amination an incipient tetrahedral oxyanion or thiolate intermediate is formed via an intramolecular attack of the primary amine to the amide/thioamide carbonyl. It undergoes either a 1,2-pyridyl shift with the retention of the carbonyl moiety or H 2 S elimination for scaffold diversification. Remarkably, inspite of a positive influence of copper in the reaction outcome, from our preliminary investigations, the benzimidazolone product was obtained in good to moderate yields in two steps under metal-free conditions. The N -pyridyl moiety of the benzimidazolone was removed for further manipulation of the free NH group.